Crystallization of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol

ABSTRACT

A method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to obtain 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form using precipitation with hexane from ethyl acetate. A method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals acceptable for X-ray experiment using precipitation with hexane from benzene by diffusive exchange of the solvents is also described.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under DK047814 awarded by the National Institutes of Health. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION

The present invention relates to purification of organic compounds, and more particularly to the purification of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (referred to herein as “051810”) by preparing it in crystalline form.

Purification of organic compounds, especially those designated for pharmaceutical use, is of considerable importance for chemists synthesizing such compounds. Preparation of the compound usually requires many synthetic steps and, therefore, the final product can be contaminated not only with side-products derived from the last synthetic step of the procedure but also with compounds that were formed in previous steps. Even chromatographic purification, which is a very efficient but relatively time-consuming process, does not usually provide compounds which are sufficiently pure to be used as drugs.

Depending on the method used to synthesize 1α-hydroxyvitamin D compounds, different minor undesirable compounds can accompany the final product. Thus, for example, if direct C-1 hydroxylation of 5,6-trans geometric isomer of vitamin D is performed, followed by SeO₂/NMO oxidation and photochemical irradiation [see Andrews et al., J. Org. Chem. 51, 1635 (1986); Calverley et al., Tetrahedron 43, 4609 (1987); Choudry et al, J. Org. Chem. 58, 1496 (1993)], the final 1α-hydroxyvitamin D product can be contaminated with 1β-hydroxy- as well as 5,6-trans isomers. If the method consists of C-1 allylic oxidation of the 4-phenyl-1,2,4-triazoline-3,5-dione adduct of the previtamin D compound, followed by cycloreversion of the modified adduct under basic conditions [Nevinćkx et al., Tetrahedron 47, 9419 (1991); Vanmaele et al, Tetrahedron 41, 141 (1985) and 40, 1179 (1994); Vanmaele et al., Tetrahedron Lett. 23. 995 (1982)], one can expect that the desired 1α-hydroxyvitamin can be contaminated with the previtamin 5(10), 6,8-triene and 1β-hydroxy isomer. One of the most useful C-1 hydroxylation methods, of very broad scope and numerous applications, is the experimentally simple procedure elaborated by Paaren et al. [see J. Org. Chem. 45, 3253 (1980) and Proc. Natl. Acad. Sci. U.S.A. 75, 2080 (1978)]. This method consists of allylic oxidation of 3,5-cyclovitamin D derivatives, readily obtained from the buffered solvolysis of vitamin D tosylates, with SeO₂/t-BuOOH and subsequent acid-catalyzed cycloreversion to the desired 1α-hydroxy compounds. Taking into account this synthetic path it is reasonable to assume that the final product can be contaminated with 1α-hydroxy epimer, 5,6-trans isomer and the previtamin D form. 1α-hydroxyvitamin D₄ is another undesirable contaminant found in 1α-hydroxyvitamin D compounds synthesized from vitamin D₂ or from ergosterol. 1α-hydroxyvitamin D₄ results from C-1 oxidation of vitamin D₄, which in turn is derived from contamination of the commercial ergosterol material. Typically, the final product may contain up to about 1.5% by weight 1α-hydroxyvitamin D₄. Thus, a purification technique that would eliminate or substantially reduce the amount of 1α-hydroxyvitamin D₄ in the final product to less than about 0.1-0.2% would be highly desirable.

The vitamin D conjugated triene system is not only heat- and light-sensitive but it is also prone to oxidation, leading to the complex mixture of very polar compounds. Oxidation usually happens when a vitamin D compound has been stored for a prolonged time. Other types of processes that can lead to a partial decomposition of vitamin D compounds consist of some water-elimination reactions; their driving force is allylic (1α-) and homoallylic (3β-) position of the hydroxy groups. The presence of such above-mentioned oxidation and elimination products can be easily detected by thin-layer chromatography.

Usually, all 1α-hydroxylation procedures require at least one chromatographic purification. However, even chromatographically purified 1α-hydroxyvitamin D compounds, although showing consistent spectroscopic data, suggesting homogeneity, do not meet the purity criteria required for therapeutic agents that can be orally, parenterally or transdermally administered. Therefore, it was evident that a suitable method of purification of the 1α-hydroxylated vitamin D compound 051810 is required.

SUMMARY OF THE INVENTION

The present invention relates to a method of purifying 051810 by means of crystallization to obtain 051810 in crystalline form. The solvent plays a crucial role in the crystallization process, and is typically an individual liquid substance or a suitable mixture of different liquids. For crystallizing 051810, the most appropriate solvent and/or solvent system is characterized by the following factors:

(1) low toxicity;

(2) low boiling point;

(3) significant dependence of solubility properties with regard to temperature (condition necessary for providing satisfactory crystallization yield); and

(4) relatively low cost.

Interestingly, hexane, so frequently used for crystallization purposes, was found less suitable as the sole solvent for crystallization of 051810. However, it was found that a mixture of ethyl acetate and hexane, was most useful for the crystallization of 051810. In particular, it was determined that a mixture of about 1% ethyl acetate with about 99% hexane (by volume) performed well. The ethyl acetate/hexane solvent mixture was also easy to remove by evaporation or other well known methods. In all cases the crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration or other means.

Accordingly, there is obtained 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form. The crystalline form and three dimensional structure of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol has a molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90°, β=90° and γ=90°.

In one embodiment, there is described a method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of:

(a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate;

(b) adding hexane to said solvent and dissolved product to form a mixture;

(c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and

(d) separating the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.

In another embodiment, there is described a method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of:

(a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene;

(b) providing a second solvent comprising hexane;

(c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and

(d) recovering the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of the three dimensional structure of the first crystallographic asymmetric molecule for 051810 as defined by the atomic positional parameters discovered and set forth herein;

FIG. 2 a is an illustration of the three dimensional structure of the second crystallographic asymmetric molecule for 051810 in the absence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein;

FIG. 2 b is an illustration of the three dimensional structure of the second asymmetric molecule for 051810 in the presence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein; and

FIG. 3 is an illustration of a ball-and-stick representation of the entire asymmetric unit for 051810.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810) in crystalline form, a pharmacologically important compound, characterized by the formula I shown below:

The present invention also provides a valuable method of purification of 051810. The purification technique involves obtaining the 051810 product in crystalline form by utilizing a crystallization procedure wherein the 051810 material to be purified is dissolved using ethyl acetate as the solvent and further precipitation with hexane. Preferably a ratio of ethyl acetate and hexane is about 1:99 (by volume). Thereafter, the solvent can be removed by evaporation, with or without vacuum, or other means as is well known, or the resultant crystals may be filtered from the mother liquor. The technique can be used to purify a wide range of final products containing 051810 obtained from any known synthesis thereof, and in varying concentrations, i.e. from microgram amounts to kilogram amounts. As is well known to those skilled in this art, the amount of solvent utilized should be minimized and/or adjusted according to the amount of 051810 to be purified.

The usefulness and advantages of the present crystallization procedure is shown in the following specific Example 1. After crystallization, the precipitated material was observed under a microscope to confirm its crystalline form. Yields of crystals were relatively high and the obtained crystals showed a relatively sharp melting point of 140-145° C.

The described crystallization process of the synthetic 051810 product represents a valuable purification method, which can remove most side products derived from the synthetic path. Such impurity is the result of the contamination of starting raw materials. The crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration, or other means.

Crystallization of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810) EXAMPLE 1 Crystallization from Ethyl Acetate/Hexane

1.25 g of prepurified (see U.S. Pat. No. 7,238,681) crude 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol was dissolved in ethyl acetate (3 ml) at room temperature and hexane (300 ml) was poured into the vigorously shaken solution. The mixture was kept in a refrigerator (at 4° C.) overnight and the resulted crystals were filtered off, washed with one portion (30 ml) of cooled (4° C.) hexane and dried under reduced pressure for 3 h giving 1.10 g of a pure product.

In order to obtain crystals acceptable for the X-ray experiment, 1α-Hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (12 mg) was placed in an inner tube of a vessel and dissolved in 300 μl of benzene. To an outer tube of the vessel hexane (2 ml) was poured so that a benzene to hexane ratio of about 13:87, by volume, is obtained, and the whole system was carefully purged with argon, and then maintained as a closed system. The vessel was kept tightly closed for 4 days at room temperature. Crystals were grown employing diffusive exchange of the two solvents.

A colorless rod-shaped crystal of dimensions 0.73×0.08×0.02 mm was selected for structural analysis. Intensity data were collected using a Bruker AXS Platinum 135 CCD detector controlled with the PROTEUM software suite (Bruker AXS Inc., Madison, Wis.). The x-ray source was CuKa radiation (1.54178 Å) from a Rigaku RU200 x-ray generator equipped with Montel optics, operated at 50 kV and 90 mA. The x-ray data were processed with SAINT version 7.06A (Bruker AXS Inc.) and internally scaled with SADABS version 2005/1 (Bruker AXS Inc.). The sample was mounted on a glass fiber using vacuum grease and cooled to 100 K. The intensity data were measured as a series of phi and omega oscillation frames each of 1° for 60-120 sec/frame. The detector was operated in 1024×1024 mode and was positioned 5.0 cm from the sample. Cell parameters were determined from a non-linear least squares fit of 9999 peaks in the range of 3.0<theta<50.8°. The data were merged to form a set of 4693 independent data with R(int)=0.0884.

The orthorhombic space group P2(1)2(1)2(1) was determined by systematic absences and statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by full-matrix least-squares methods on F², (a) G. M. Sheldrick (1994), SHELXTL Version 5 Reference Manual, Bruker AXS Inc.; (b) International Tables for Crystallography, Vol. C, Kluwer: Boston (1995). The asymmetric unit is comprised of two molecules of 051810 and a benzene molecule. Molecule “A” is shown in FIG. 1, with thermal ellipsoids drawn at the 40% probability level. Based on lattice packing, the benzene molecule could not be present at full occupancy, and refinement of its occupancy led to a value of approximately 0.5. The presence of the benzene molecule lead to a disorder in a portion of molecule “B”. Refinement of the occupancies of the two disordered configurations independently of the occupancy of the benzene converged also at a value of about 0.5 for each. FIG. 2 a shows molecule B in its configuration in the absence of the benzene molecule, and FIG. 2 b shows its configuration in the presence of the benzene molecule; both figures are drawn with thermal ellipsoids at the 40% probability level. FIG. 3 shows a ball-and-stick representation of the entire asymmetric unit, with the hollow bonds showing the conformation in the presence of the benzene molecule. Hydrogen atom positions were refined by a riding model with idealized geometry. Non-hydrogen atoms were refined with anisotropic displacement parameters. The benzene molecule was refined with idealized geometry. A total of 559 parameters were refined against 26 restraints and 4693 data to give wR2=0.2524 and S=0.951 for weights of w=1/[s²(F²)+(0.1719P)²], where P=[F_(o) ²+2F_(c) ²]/3. The final R(F) was 0.0910 for the 6781 observed data. The largest shift/s.u. was 0.001 in the final refinement cycle and the final difference map had maxima and minima of 0.366 and −0.305 e/Å³, respectively. The absolute structure was determined by refinement of the Flack parameter, H. D. Flack, Acta Cryst. A, vol. 39, 876-881 (1983).

The three dimensional structure of 051810 as defined by the following physical data and atomic positional parameters described and calculated herein is illustrated in FIGS. 1, 2 a, 2 b and 3.

TABLE 1 Crystal data and structure refinement for 051810. Identification Code 051810 Empirical formula C45 H67 O4 Formula weight 671.99 Temperature 100(1) K Wavelength 1.54178 Å Crystal system Orthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = 4.8020(10) Å α = 90° b = 22.940(5) Å β = 90° c = 36.124(7) Å γ = 90° Volume 3979.3(14) Å³ Z 4 Density (calculated) 1.122 Mg/m³ Absorption coefficient 0.533 mm⁻¹ F(000) 1476 Crystal 0.73 × 0.08 × 0.02 mm Theta range for data collection 2.28 to 54.17° Limiting indices −4 < h < 4, −24 < k < 23, −37 < 1 < 37 Reflections collected 12592 Independent reflections 4693 [R(int) = 0.0884] Completeness to Theta = 54.17° 98.2% Refinement method Full-matrix least-squares on F² Data/restraints/parameters 4693/26/559 Goodness-of-fit on F² 0.951 Final R indices [I > 2σ(I)] R1 = 0.0910, wR2 = 0.2214 R indices (all data) R1 = 0.1268, wR2 = 0.2524 Extinction coefficient 0.0124(12) Largest diff. peak and hole 0.366 and −0.305 e/A³ Melting Point 140-145° C.

TABLE 2 Atomic coordinates (× 10⁴) and equivalent isotropic displacement parameters (Å² × 10³] for 051810. U(eq) is defined as one third of the trace of the orthogonalized U_(ij) tensor. X y z U(eq) O(1A) −322(12) 7615(2) 6913(2) 59(2) O(3A) −2739(11)  9404(2) 7179(1) 51(1) C(10A) −165(18) 8424(3) 6486(2) 47(2) C(1A) −994(17) 8232(3) 6868(2) 46(2) C(3A)  148(16) 9249(3) 7108(2) 49(2) C(14A) −7331(19)  8940(3) 5377(2) 48(2) C(4A)  864(18) 9437(3) 6719(2) 49(2) C(13A) −6378(17)  9119(3) 4990(2) 42(2) C(7A) −4130(18)  9025(3) 5916(2) 50(2) C(17A) −7691(17)  8673(3) 4726(2) 47(2) C(2A)  472(16) 8595(3) 7156(2) 47(2) C(15A) −7129(18)  8276(3) 5360(2) 49(2) C(8A) −5795(16)  9274(3) 5667(2) 43(2) C(9A) −6387(19)  9924(3) 5624(2) 52(2) C(12A) −7120(18)  9770(3) 4931(2) 46(2) C(5A) −649(16) 9072(3) 6439(2) 43(2) C(16A) −8423(18)  8158(3) 4986(2) 50(2) C(21A) −4792(18)  9008(3) 4177(2) 48(2) C(20A) −5793(17)  8486(3) 4408(2) 45(2) C(11A) −5708(19)  10137(3)  5234(2) 51(2) C(6A) −2416(17)  9326(3) 6193(2) 47(2) C(22A) −7262(18)  8050(3) 4144(2) 55(2) C(2A′) 1940(20) 8381(4) 7432(2) 76(3) O(3B) −3150(11)  10326(2)  7677(1) 48(1) O(1B) −4693(10)  12069(2)  8071(1) 40(1) C(1B) −4362(16)  11592(3)  7816(2) 39(2) C(2B) −6068(16)  11074(3)  7930(2) 40(2) C(10B) −5147(19)  11778(3)  7423(2) 49(2) C(3B) −5950(17)  10575(3)  7667(2) 46(2) C(4B) −6576(18)  10759(3)  7270(2) 48(2) C(6B) −3204(17)  11254(3)  6861(2) 51(2) C(5B) −4833(17)  11275(3)  7155(2) 44(2) C(7B) −1376(17)  11745(4)  6734(2) 58(2) C(2B′) −7707(19)  11071(3)  8221(2) 56(2) C(8B)  259(18) 11713(5)  6435(3) 75(3) C(12B) 2040(50) 12137(10) 5703(5) 105(13) C(9B)  720(60) 11337(11) 6171(5) 65(7) C(14B) 1730(40) 12297(7)  6369(5) 66(5) C(13B) 1580(50) 12609(9)  5997(5) 86(8) C(11B)  420(50) 11584(11) 5782(5)  96(11) C(15B) 1870(60) 12851(8)  6602(7) 111(14) C(17B) 3160(40) 13190(9)  5995(8) 109(12) C(16B) 3350(40) 13356(9)  6404(7) 101(9)  C(20B) 2050(50) 13662(10) 5735(7) 151(15) C(22B) 3890(50) 14206(10) 5741(8) 185(18) C (21B)  1610(120) 13442(14) 5339(8) 230(30) C(12′) 1350(40) 11726(7)  5609(6) 45(6) C(9′)  160(70) 11067(10) 6145(6) 46(8) C(14′) 2290(40) 12120(8)  6246(4) 45(8) C(13′) 1240(50) 12265(7)  5860(4) 36(6) C(11′) −560(50) 11251(8)  5752(5) 39(6) C(15′) 2350(40) 12687(8)  6459(5) 33(5) C(17′) 2980(40) 12809(6)  5789(4) 38(5) C(16′) 3750(40) 13067(7)  6167(4) 35(6) C(20′) 1650(50) 13270(7)  5543(5) 72(8) C(22′) 3670(70) 13750(10) 5428(8) 78(9) C(21′)   80(60) 13041(10) 5206(6) 76(9) C(1) 1350(20) 14678(5)  6378(3) 67(5) C(2) 1060(20) 14340(5)  6695(4) 64(5) C(3) 3410(30) 14137(4)  6879(2) 69(5) C(4) 6050(20) 14270(4)  6746(3) 58(5) C(5) 6340(20) 14608(4)  6429(3) 62(5) C(6) 3990(30) 14811(4)  6245(3) 74(6)

TABLE 3 Bondlengths [Å] for 051810. O(1A)—C(1A) 1.460(8) O(1A)—H(1AA) 0.8200 O(3A)—C(3A) 1.454(9) O(3A)—H(3AA) 0.8200 C(10A)—C(1A) 1.502(9) C(10A)—C(5A) 1.513(10) C(10A)—H(10A) 0.9700 C(10A)—H(10B) 0.9700 C(1A)—C(2A) 1.508(11) C(1A)—H(1AB) 0.9800 C(3A)—C(4A) 1.507(10) C(3A)—C(2A) 1.518(10) C(3A)—H(3AB) 0.9800 C(14A)—C(8A) 1.492(10) C(14A)—C(13A) 1.527(10) C(14A)—C(15A) 1.529(9) C(14A)—H(14A) 0.9800 C(4A)—C(5A) 1.501(10) C(4A)—H(4AA) 0.9700 C(4A)—H(4AB) 0.9700 C(13A)—C(17A) 1.534(10) C(13A)—C(12A) 1.550(9) C(13A)—H(13A) 0.9800 C(7A)—C(8A) 1.332(10) C(7A)—C(6A) 1.469(10) C(7A)—H(7AA) 0.9300 C(17A)—C(20A) 1.529(10) C(17A)—C(16A) 1.548(10) C(17A)—H(17A) 0.9800 C(2A)—C(2A′) 1.314(11) C(15A)—C(16A) 1.511(10) C(15A)—H(15A) 0.9700 C(15A)—H(15B) 0.9700 C(8A)—C(9A) 1.526(10) C(9A)—C(11A) 1.528(9) C(9A)—H(9AA) 0.9700 C(9A)—H(9AB) 0.9700 C(12A)—C(11A) 1.538(10) C(12A)—H(12A) 0.9700 C(12A)—H(12B) 0.9700 C(5A)—C(6A) 1.359(10) C(16A)—H(16A) 0.9700 C(16A)—H(16B) 0.9700 C(21A)—C(20A) 1.536(10) C(21A)—H(21A) 0.9600 C(21A)—H(21B) 0.9600 C(21A)—H(21C) 0.9600 C(20A)—C(22A) 1.552(10) C(20A)—H(20A) 0.9800 C(11A)—H(11A) 0.9700 C(11A)—H(11B) 0.9700 C(6A)—H(6AA) 0.9300 C(22A)—H(22A) 0.9600 C(22A)—H(22B) 0.9600 C(22A)—H(22C) 0.9600 C(2A′)—H(1A′) 0.9300 C(2A′)—H(2A′) 0.9300 O(3B)—C(3B) 1.461(10) O(3B)—H(3BA) 0.8200 O(1B)—C(1B) 1.439(8) O(1B)—H(1BA) 0.8200 C(1B)—C(2B) 1.501(10) C(1B)—C(10B) 1.532(9) C(1B)—H(1BB) 0.9800 C(2B)—C(2B′) 1.313(10) C(2B)—C(3B) 1.488(10) C(10B)—C(5B) 1.514(9) C(10B)—H(10C) 0.9700 C(10B)—H(10D) 0.9700 C(3B)—C(4B) 1.526(7) C(3B)—H(3BB) 0.9800 C(4B)—C(5B) 1.506(10) C(4B)—H(4BA) 0.9700 C(4)—H(4BB) 0.9700 C(6B)—C(5B) 1.321(10) C(6B)—C(7B) 1.499(8) C(6B)—H(6BA) 0.9300 C(7B)—C(8B) 1.338(12) C(7B)—H(7BA) 0.9300 C(2B′)—H(1B′) 0.9300 C(2B′)—H(2B′) 0.9300 C(8B)—C(9B) 1.50(2) C(8B)—C(14′) 1.514(10) C(8B)—C(14B) 1.534(10) C(8B)—C(9′) 1.52(2) C(12B)—C(11B) 1.516(10) C(12B)—C(13B) 1.534(10) C(12B)—H(12C) 0.9700 C(12B)—H(12D) 0.9700 C(9B)—C(11B) 1.522(10) C(9B)—H(9BA) 0.9700 C(9B)—H(9BB) 0.9700 C(14B)—C(15B) 1.527(10) C(14B)—C(13B) 1.524(10) C(14B)—H(14B) 0.9800 C(13B)—C(17B) 1.532(10) C(13B)—H(13B) 0.9800 C(11B)—H(11C) 0.9700 C(11B)—H(11D) 0.9700 C(15B)—C(16B) 1.535(10) C(15B)—H(15C) 0.9700 C(15B)—H(15D) 0.9700 C(17B)—C(16B) 1.528(10) C(17B)—C(20B) 1.528(10) C(17B)—H(17B) 0.9800 C(16B)—H(16C) 0.9700 C(16B)—H(16D) 0.9700 C(20B)—C(22B) 1.528(10) C(20B)—C(21B) 1.532(11) C(20B)—H(20B) 0.9800 C(22B)—H(22D) 0.9600 C(22B)—H(22E) 0.9600 C(22B)—H(22F) 0.9600 C(21B)—H(21D) 0.9600 C(21B)—H(21E) 0.9600 C(21B)—H(21F) 0.9600 C(12′)—C(11′) 1.513(10) C(12′)—C(13′) 1.534(10) C(12′)—H(12E) 0.9700 C(12′)—H(12F) 0.9700 C(9′)—C(11′) 1.519(10) C(9′)—H(9BC) 0.9700 C(9′)—H(9BD) 0.9700 C(14′)—C(15′) 1.512(10) C(14′)—C(13′) 1.517(10) C(14′)—H(14′) 0.9800 C(13′)—C(17′) 1.523(10) C(13′)—H(13′) 0.9800 C(11′)—H(11E) 0.9700 C(11′)—H(11F) 0.9700 C(15′)—C(16′) 1.524(10) C(15′)—H(15E) 0.9700 C(15′)—H(15F) 0.9700 C(17′)—C(20′) 1.523(10) C(17′)—C(16′) 1.533(10) C(17′)—H(17′) 0.9800 C(16′)—H(16E) 0.9700 C(16′)—H(16F) 0.9700 C(20′)—C(21′) 1.525(10) C(20′)—C(22′) 1.528(10) C(20′)—H(20C) 0.9800 C(22′)—H(22G) 0.9600 C(22′)—H(22H) 0.9600 C(22′)—H(22I) 0.9600 C(21′)—H(21G) 0.9600 C(21′)—H(21H) 0.9600 C(21′)—H(21I) 0.9600 C(1)—C(2) 1.3900 C(1)—C(6) 1.3900 C(1)—H(1A) 0.9300 C(2)—C(3) 1.3900 C(2)—H(2A) 0.9300 C(3)—C(4) 1.3900 C(3)—H(3A) 0.9300 C(4)—C(5) 1.3900 C(4)—H(4A) 0.9300 C(5)—C(6) 1.3900 C(5)—H(5A) 0.9300 C(6)—H(6A) 0.9300

TABLE 4 Bond angles [°] for 051810. C(1A)—O(1A)—H(1AA) 109.5 C(3A)—O(3A)—H(3AA) 109.5 C(1A)—C(10A)—C(5A) 110.6(6) C(1A)—C(10A)—H(10A) 109.7 C(5A)—C(10A)—H(10A) 109.6 C(1A)—C(10A)—H(10B) 109.4 C(5A)—C(10A)—H(10B) 109.4 H(10A)—C(10A)—H(10B) 108.1 O(1A)—C(1A)—C(10A) 109.1(6) O(1A)—C(1A)—C(2A) 110.9(6) C(10A)—C(1A)—C(2A) 110.4(6) O(1A)—C(1A)—H(1AB) 108.8 C(10A)—C(1A)—H(1AB) 108.8 C(2A)—C(1A)—H(1AB) 108.8 O(3A)—C(3A)—C(4A) 108.2(6) O(3A)—C(3A)—C(2A) 108.6(6) C(4A)—C(3A)—C(2A) 111.5(6) O(3A)—C(3A)—H(3AB) 109.5 C(4A)—C(3A)—H(3AB) 109.5 C(2A)—C(3A)—H(3AB) 109.5 C(8A)—C(14A)—C(13A) 110.9(7) C(8A)—C(14A)—C(15A) 120.6(7) C(13A)—C(14A)—C(15A) 102.2(6) C(8A)—C(14A)—H(14A) 107.5 C(13A)—C(14A)—H(14A) 107.5 C(15A)—C(14A)—H(14A) 107.6 C(5A)—C(4A)—C(3A) 111.0(6) C(5A)—C(4A)—H(4AA) 109.4 C(3A)—C(4A)—H(4AA) 109.4 C(5A)—C(4A)—H(4AB) 109.4 C(3A)—C(4A)—H(4AB) 109.5 H (4AA)—C(4A)—H(4AB) 108.0 C(14A)—C(13A)—C(17A) 105.5(6) C(14A)—C(13A)—C(12A) 108.4(6) C(17A)—C(13A)—C(12A) 117.6(6) C(14A)—C(13A)—H(13A) 108.4 C(17A)—C(13A)—H(13A) 108.3 C(12A)—C(13A)—H(13A) 108.4 C(8A)—C(7A)—C(6A) 126.6(7) C(8A)—C(7A)—H(7AA) 116.8 C(6A)—C(7A)—H(7AA) 116.6 C(20A)—C(17A)—C(13A) 114.2(7) C(20A)—C(17A)—C(16A) 112.1(6) C(13A)—C(17A)—C(16A) 103.1(5) C(20A)—C(17A)—H(17A) 109.1 C(13A)—C(17A)—H(17A) 109.1 C(16A)—C(17A)—H(17A) 109.1 C(2A′)—C(2A)—C(1A) 124.4(7) C(2A′)—C(2A)—C(3A) 120.9(8) C(1A)—C(2A)—C(3A) 114.7(6) C(16A)—C(15A)—C(14A) 100.9(6) C(16A)—C(15A)—H(15A) 111.6 C(14A)—C(15A)—H(15A) 111.6 C(16A)—C(15A)—H(15B) 111.6 C(14A)—C(15A)—H(15B) 111.5 H(15A)—C(15A)—H(15B) 109.4 C(7A)—C(8A)—C(14A) 123.4(6) C(7A)—C(8A)—C(9A) 126.8(7) C(14A)—C(8A)—C(9A) 109.8(6) C(11A)—C(9A)—C(8A) 111.5(6) C(11A)—C(9A)—H(9AA) 109.3 C(8A)—C(9A)—H(9AA) 109.4 C(11A)—C(9A)—H(9AB) 109.3 C(8A)—C(9A)—H(9AB) 109.4 H(9AA)—C(9A)—H(9AB) 108.0 C(11A)—C(12A)—C(13A) 109.2(6) C(11A)—C(12A)—H(12A) 109.8 C(13A)—C(12A)—H(12A) 109.8 C(11A)—C(12A)—H(12B) 109.9 C(13A)—C(12A)—H(12B) 109.8 H(12A)—C(12A)—H(12B) 108.3 C(6A)—C(5A)—C(4A) 120.2(6) C(6A)—C(5A)—C(10A) 126.2(7) C(4A)—C(5A)—C(10A) 113.4(6) C(15A)—C(16A)—C(17A) 108.1(6) C(15A)—C(16A)—H(16A) 110.1 C(17A)—C(16A)—H(16A) 110.1 C(15A)—C(16A)—H(16B) 110.0 C(17A)—C(16A)—H(16B) 110.1 H(16A)—C(16A)—H(16B) 108.4 C(20A)—C(21A)—H(21A) 109.6 C(20A)—C(21A)—H(21B) 109.4 H(21A)—C(21A)—H(21B) 109.5 C(20A)—C(21A)—H(21C) 109.4 H(21A)—C(21A)—H(21C) 109.5 H(21B)—C(21A)—H(21C) 109.5 C(17A)—C(20A)—C(21A) 112.2(6) C(17A)—C(20A)—C(22A) 111.9(7) C(21A)—C(20A)—C(22A) 108.1(6) C(17A)—C(20A)—H(20A) 108.2 C(21A)—C(20A)—H(20A) 108.2 C(22A)—C(20A)—H(20A) 108.2 C(9A)—C(11A)—C(12A) 112.8(7) C(9A)—C(11A)—H(11A) 109.0 C(12A)—C(11A)—H(11A) 109.0 C(9A)—C(11A)—H(11B) 109.1 C(12A)—C(11A)—H(11B) 109.0 H(11A)—C(11A)—H(11B) 107.8 C(5A)—C(6A)—C(7A) 126.5(7) C(5A)—C(6A)—H(6AA) 116.8 C(7A)—C(6A)—H(6AA) 116.7 C(20A)—C(22A)—H(22A) 109.4 C(20A)—C(22A)—H(22B) 109.5 H(22A)—C(22A)—H(22B) 109.5 C(20A)—C(22A)—H(22C) 109.5 H(22A)—C(22A)—H(22C) 109.5 H(22B)—C(22A)—H(22C) 109.5 C(2A)—C(2A′)—H(1A′) 120.0 C(2A)—C(2A′)—H(2A′) 120.0 H(1A′)—C(2A′)—H(2A′) 120.0 C(3B)—O(3B)—H(3BA) 109.4 C(1B)—O(1B)—H(1BA) 109.4 O(1B)—C(1B)—C(2B) 111.5(5) O(1B)—C(1B)—C(10B) 110.7(5) C(2B)—C(1E)—C(10B) 110.0(6) O(1B)—C(1B)—H(1BB) 108.2 C(2B)—C(1B)—H(1BB) 108.2 C(10B)—C(1B)—H(1BB) 108.2 C(2B′)—C(2B)—C(3B) 122.1(7) C(2B′)—C(2B)—C(1B) 123.4(7) C(3B)—C(2B)—C(1B) 114.4(6) C(5B)—C(10B)—C(1B) 110.8(6) C(5B)—C(10B)—H(10C) 109.6 C(1B)—C(10B)—H(10C) 109.5 C(5B)—C(10B)—H(10D) 109.4 C(1B)—C(10B)—H(10D) 109.5 H(10C)—C(10B)—H(10D) 108.1 O(3B)—C(3B)—C(2B) 108.7(6) O(3B)—C(3B)—C(4B) 108.2(6) C(2B)—C(3B)—C(4B) 112.4(6) O(3B)—C(3B)—H(3BB) 109.1 C(2B)—C(3B)—H(3BB) 109.2 C(4B)—C(3B)—H(3BB) 109.2 C(5B)—C(4B)—C(3B) 111.5(6) C(5B)—C(4B)—H(4BA) 109.3 C(3B)—C(4B)—H(4BA) 109.2 C(5B)—C(4B)—H(4BB) 109.4 C(3B)—C(4B)—H(4BB) 109.4 H(4BA)—C(4B)—H(4BB) 108.0 C(5B)—C(68)—C(7B) 124.5(7) C(5B)—C(6B)—H(6BA) 117.8 C(7B)—C(6B)—H(6BA) 117.7 C(6B)—C(5B)—C(4B) 121.5(6) C(6B)—C(5B)—C(10B) 126.9(7) C(4B)—C(5B)—C(10B) 111.6(6) C(8B)—C(7B)—C(6B) 123.3(8) C(8B)—C(7B)—H(7BA) 118.3 C(6B)—C(7B)—H(7BA) 118.4 C(2B)—C(2B′)—H(1B′) 120.1 C(2B)—C(2B′)—H(2B′) 119.9 H(1B′)—C(2B′)—H(2B′) 120.0 C(9B)—C(8B)—C(7B) 136.7(13) C(9B)—C(8B)—C(14′) 88.1(14) C(7B)—C(8B)—C(14′) 135.1(12) C(9B)—C(8B)—C(14B) 112.6(15) C(7B)—C(8B)—C(14B) 110.4(11) C(14′)—C(8B)—C(14B) 24.9(8) C(9B)—C(8B)—C(9′) 16.9(16) C(7B)—C(8B)—C(9′) 119.8(12) C(14′)—C(8B)—C(9′) 105.0(13) C(14B)—C(8B)—C(9′) 129.4(13) C(11B)—C(12B)—C(13B) 112.7(18) C(11B)—C(12B)—H(12C) 108.9 C(13B)—C(12B)—H(12C) 108.6 C(11B)—C(12B)—H(12D) 109.3 C(13B)—C(12B)—H(12D) 109.5 H(12C)—C(12B)—H(12D) 107.8 C(8B)—C(9B)—C(11B) 114.4(19) C(8B)—C(9B)—H(9BA) 109.1 C(11B)—C(9B)—H(9BA) 108.4 C(8B)—C(9B)—H(9BB) 108.6 C(11B)—C(9B)—H(9BB) 108.6 H(9BA)—C(9B)—H(9BB) 107.6 C(15B)—C(14B)—C(13B) 95.5(15) C(15B)—C(14B)—C(8B) 131.5(13) C(13B)—C(14B)—C(8B) 121.8(14) C(15B)—C(14B)—H(14B) 100.6 C(13B)—C(14B)—H(14B) 101.3 C(8B)—C(14B)—H(14B) 101.0 C(14B)—C(13B)—C(17B) 113.0(14) C(14B)—C(13B)—C(12B) 105.8(15) C(17B)—C(13B)—C(12B) 122.6(18) C(14B)—C(13B)—H(13B) 104.3 C(17B)—C(13B)—H(13B) 104.4 C(12B)—C(13B)—H(13B) 105.0 C(12B)—C(11B)—C(9B) 115.9(19) C(12B)—C(11B)—H(11C) 108.0 C(9B)—C(11B)—H(11C) 108.5 C(12B)—C(11B)—H(11D) 108.5 C(9B)—C(11B)—H(11D) 108.3 H(11C)—C(11B)—H(11D) 107.4 C(14B)—C(15B)—C(16B) 113.1(17) C(14B)—C(15B)—H(15C) 109.4 C(16B)—C(15B)—H(15C) 109.8 C(14B)—C(15B)—H(15D) 107.9 C(16B)—C(15B)—H(15D) 108.7 H(15C)—C(15B)—H(15D) 107.6 C(16B)—C(17B)—C(20B) 115.9(19) C(16B)—C(17B)—C(13B) 104.0(16) C(20B)—C(17B)—C(13B) 116.6(16) C(16B)—C(17B)—H(17B) 106.2 C(20B)—C(17B)—H(17B) 106.6 C(13B)—C(17B)—H(17B) 106.7 C(17B)—C(16B)—C(15B) 103.5(18) C(17B)—C(16B)—H(16C) 111.1 C(15B)—C(16B)—H(16C) 110.8 C(17B)—C(16B)—H(16D) 111.7 C(15B)—C(16B)—H(16D) 110.5 H(16C)—C(16B)—H(16D) 109.2 C(22B)—C(20B)—C(17B) 111.7(17) C(22B)—C(20B)—C(21B) 111(2)   C(17B)—C(20B)—C(21B) 113(2)   C(22B)—C(20B)—2(20B) 107.2 C(17B)—C(20B)—H(20B) 107.2 C(21B)—C(20B)—H(20B) 106.3 C(20B)—C(22B)—H(22D) 109.5 C(20B)—C(22B)—H(22E) 109.5 H(22D)—C(22B)—H(22E) 109.5 C(20B)—C(22B)—H(22F) 109.3 H(22D)—C(22B)—H(22F) 109.5 H(22E)—C(22B)—H(22F) 109.5 C(20B)—C(21B)—H(21D) 110.2 C(20B)—C(21B)—H(21E) 109.4 H(21D)—C(21B)—H(21E) 109.5 C(20B)—C(21B)—H(21F) 108.8 H(21D)—C(21B)—H(21F) 109.5 H(21E)—C(21B)—H(21F) 109.5 C(11′)—C(12′)—C(13′) 111.0(13) C(11′)—C(12′)—H(12E) 109.4 C(13′)—C(12′)—H(12E) 109.7 C(11′)—C(12′)—H(12F) 109.8 C(13′)—C(12′)—H(12F) 108.9 H(12E)—C(12′)—H(12F) 108.0 C(11′)—C(9′)—C(8B) 108.5(15) C(11′)—C(9′)—H(9BC) 110.2 C(8B)—C(9′)—H(9BC) 109.7 C(11′)—C(9′)—H(9BD) 109.9 C(8B)—C(9′)—H(9BD) 110.3 H(9BC)—C(9′)—H(9BD) 108.3 C(8B)—C(14′)—C(15′) 108.3(13) C(8B)—C(14′)—C(13′) 109.7(13) C(15′)—C(14′)—C(13′) 106.5(15) C(8B)—C(14′)—H(14′) 111.1 C(15′)—C(14′)—H(14′) 110.6 C(13′)—C(14′)—H(14′) 110.5 C(14′)—C(13′)—C(17′) 98.8(11) C(14′)—C(13′)—C(12′) 110.8(17) C(17′)—C(13′)—C(12′) 122.8(15) C(14′)—C(13′)—H(13′) 107.9 C(17′)—C(13′)—H(13′) 107.7 C(12′)—C(13′)—H(13′) 107.8 C(12′)—C(11′)—C(9′) 112.5(18) C(12′)—C(11′)—H(11E) 108.6 C(9′)—C(11′)—H(11E) 108.7 C(12′)—C(11′)—H(11F) 109.6 C(9′)—C(11′)—H(11F) 109.5 H(11E)—C(11′)—H(11F) 107.9 C(14′)—C(15′)—C(16′) 98.5(12) C(14′)—C(15′)—H(15E) 112.0 C(16′)—C(15′)—H(15E) 112.7 C(14′)—C(15′)—H(15F) 111.7 C(16′)—C(15′)—H(15F) 111.9 H(15E)—C(15′)—H(15F) 109.7 C(20′)—C(17′)—C(13′) 115.8(13) C(20′)—C(17′)—C(16′) 110.6(13) C(13′)—C(17′)—C(16′) 107.3(13) C(20′)—C(17′)—H(17′) 107.9 C(13′)—C(17′)—H(17′) 107.4 C(16′)—C(17′)—H(17′) 107.5 C(15′)—C(16′)—C(17′) 106.8(14) C(15′)—C(16′)—H(16E) 109.9 C(17′)—C(16′)—H(16E) 110.7 C(15′)—C(16′)—H(16F) 110.1 C(17′)—C(16′)—H(16F) 110.8 H(16E)—C(16′)—H(16F) 108.6 C(17′)—C(20′)—C(21′) 115.7(14) C(17′)—C(20′)—C(22′) 112.9(18) C(21′)—C(20′)—C(22′) 110(2)   C(17′)—C(20′)—H(20C) 105.6 C(21′)—C(20′)—H(20C) 105.5 C(22′)—C(20′)—H(20C) 105.8 C(20′)—C(22′)—H(22G) 109.6 C(20′)—C(22′)—H(22H) 109.7 H(22G)—C(22′)—H(22H) 109.5 C(20′)—C(22′)—H(22I) 109.1 H(22G)—C(22′)—H(22I) 109.5 H(22H)—C(22′)—H(22I) 109.5 C(20′)—C(21′)—H(21G) 109.3 C(20′)—C(21′)—H(21H) 109.7 H(21G)—C(21′)—H(21H) 109.5 C(20′)—C(21′)—H(21I) 109.5 H(21G)—C(21′)—H(21I) 109.5 H(21H)—C(21′)—H(21I) 109.5 C(2)—C(1)—C(6) 120.0 C(2)—C(1)—H(1A) 120.0 C(6)—C(1)—H(1A) 120.0 C(1)—C(2)—C(3) 120.0 C(1)—C(2)—H(2A) 120.0 C(3)—C(2)—H(2A) 120.0 C(2)—C(3)—C(4) 120.0 C(2)—C(3)—H(3A) 120.0 C(4)—C(3)—H(3A) 120.0 C(5)—C(4)—C(3) 120.0 C(5)—C(4)—H(4A) 120.0 C(3)—C(4)—H(4A) 120.0 C(4)—C(5)—C(6) 120.00(5) C(4)—C(5)—H(5A) 120.0 C(6)—C(5)—H(5A) 120.0 C(5)—C(6)—C(1) 120.0 C(5)—C(6)—H(6A) 120.0 C(1)—C(6)—H(6A) 120.0

TABLE 5 Anisotropic displacement parameters [Å² × 10³] for 051810. U₁₁ U₂₂ U₃₃ U₂₃ U₁₃ U₁₂ O (1A) 50 (4) 34 (3) 93 (4) 21 (3) 2 (3) 9 (3) O (3A) 41 (4) 48 (3) 64 (3) −2 (3) 7 (3) 6 (3) C (10A) 53 (6) 33 (4) 54 (5) −5 (3) −2 (4)  −4 (4)  C (1A) 35 (5) 27 (4) 76 (5) 12 (4) 3 (4) 5 (3) C (3A) 37 (5) 36 (4) 75 (5) −2 (4) −6 (4)  4 (4) C (14A) 53 (6) 36 (4) 56 (5)  3 (4) 0 (4) 6 (4) C (4A) 50 (6) 36 (4) 61 (5)  7 (4) 0 (4) −6 (4)  C (13A) 42 (5) 35 (4) 50 (4)  8 (3) 4 (4) 9 (4) C (7A) 60 (6) 35 (4) 55 (5) −8 (4) 13 (4)  −9 (4)  C (17A) 42 (5) 45 (4) 52 (5)  7 (4) −3 (4)  3 (4) C (2A) 41 (5) 50 (5) 50 (4) 12 (4) 8 (4) 4 (4) C (15A) 52 (6) 39 (4) 58 (5)  8 (4) 6 (4) 0 (4) C (8A) 44 (5) 35 (4) 50 (5)  8 (4) 4 (4) 6 (4) C (9A) 53 (6) 47 (5) 56 (5)  2 (4) 10 (4)  1 (4) C (12A) 54 (6) 36 (4) 46 (4)  6 (3) 2 (4) 9 (4) C (5A) 36 (5) 39 (4) 55 (4)  0 (4) 4 (4) 1 (4) C (16A) 43 (5) 44 (5) 62 (5)  4 (4) −3 (4)  2 (4) C (21A) 48 (6) 43 (4) 53 (4)  1 (4) 2 (4) 10 (4)  C (20A) 39 (5) 38 (4) 57 (5)  1 (4) −1 (4)  4 (4) C (11A) 59 (6) 40 (4) 53 (5)  4 (4) 3 (4) 5 (4) C (6A) 50 (5) 33 (4) 60 (5)  2 (4) 8 (4) −3 (4)  C (22A) 59 (6) 47 (5) 59 (5)  0 (4) −12 (4)   −1 (4)  C (2A′) 77 (8) 78 (6) 74 (6) −4 (5) −5 (5)  33 (6)  O (3B) 49 (4) 34 (3) 60 (3) −1 (2) −3 (3)  4 (2) O (1B) 48 (3) 31 (3) 41 (3) −5 (2) −3 (2)  4 (2) C (1B) 44 (5) 28 (4) 45 (4) −2 (3) −1 (3)  −4 (3)  C (2B) 37 (5) 42 (4) 41 (4) −3 (3) 0 (3) −4 (3)  C (10B) 54 (6) 38 (4) 56 (5) −3 (4) 3 (4) −3 (4)  C (3B) 49 (5) 32 (4) 57 (5) −6 (4) 0 (4) −3 (4)  C (4B) 49 (5) 39 (4) 55 (5) −10 (4)  3 (4) −2 (4)  C (6B) 49 (6) 55 (5) 48 (5) −6 (4) −4 (4)  10 (4)  C (5B) 45 (5) 36 (4) 51 (4) −10 (3)  −3 (4)  10 (4)  C (7B) 38 (5) 79 (6) 57 (5) 15 (4) 1 (4) 12 (5)  C (2B′) 59 (6) 42 (5) 66 (5) −1 (4) 1 (5) 4 (4) C (8B) 33 (6) 124 (9)  68 (6) 37 (7) 6 (5) 28 (6)  C (12B)  83 (18) 190 (30)  43 (14)  64 (16) 31 (12) 80 (20) C (9B)  43 (13) 100 (20)  48 (13)   5 (13) −7 (9)   8 (16) C (14B)  16 (11) 118 (13)  63 (11)  38 (10) 26 (8)  27 (10) C (13B)  74 (16) 109 (19)  74 (15)  40 (15) 38 (13) 44 (15) C (11B)  32 (16) 170 (40)  89 (19)  40 (20) 22 (12) 20 (17) C (15B)  44 (14) 140 (30) 150 (30) 110 (20) 30 (20) 20 (20) C (17B)   9 (12)  87 (19) 230 (30)  70 (20) −3 (15) 13 (11) C (16B)  50 (13)  84 (15) 170 (20)  66 (17)  0 (13) −1 (11) C (20B) 110 (20) 140 (30) 200 (30) 120 (30) 70 (20) 90 (20) C (22B) 120 (20) 140 (20) 300 (40) 140 (30) 130 (30)  51 (19) C (21B) 410 (90) 170 (50) 120 (30) 100 (40) 100 (50)  100 (50)  C (12′)  44 (15) 10 (9)  82 (17) −11 (11)  3 (11) 0 (9) C (9′)  38 (17)  23 (13)  77 (17)  −8 (11) −5 (11) −1 (10) C (14′)  18 (16)  64 (14)  53 (16)  17 (12) 35 (12) 35 (12) C (13′)  50 (16)  34 (14)  26 (13) −8 (9)  2 (11)  0 (12) C (11′)  34 (14)  42 (12)  41 (11) −8 (9) 0 (9) −22 (9)   C (15′)  15 (13) 44 (9)  39 (10) 12 (7) 5 (7) −3 (8)  C (17′)  44 (13)  13 (11)  56 (12)  2 (9) −7 (10) −4 (9)  C (16′)  37 (14)  14 (10)  56 (13) −22 (10) −7 (11) 12 (9)  C (20′) 130 (20)  48 (17)  42 (14)  −7 (13) −1 (15) −9 (16) C (22′) 160 (30)  31 (13)  46 (14)   5 (11) 35 (15) −24 (14)  C (21′) 120 (20)  49 (15)  56 (14)  18 (11) −35 (14)   9 (14) C (1)  55 (14)  51 (11)  95 (14)  −8 (10)  2 (10) 11 (9) C (2)  62 (14)  50 (10)  80 (13) −31 (10) 15 (10)  9 (10) C (3)  83 (16)  53 (10)  71 (12) −10 (9)  12 (12) −1 (11) C (4)  63 (13) 36 (9)  74 (12) −12 (8)  3 (9) 4 (9) C (5)  91 (15) 30 (9)  67 (12)  7 (8)  7 (11) 3 (9) C (6)  87 (17)  49 (11)  85 (13)  −1 (10)  7 (13) 11 (11) The anisotropic displacement factor exponent takes the form: −2π² [h²a*²U₁₁ + . . . + 2hka*b*U₁₂]

TABLE 6 Hydrogen coordinates (×10⁴) and isotropic displacement parameters (Å² × 10³) for 051810. x y z U(eq) H(1AA) −772 7508 7121 88 H(3AA) −3165 9304 7389 76 H(10A) −1247 8212 6304 56 H(10B) 1787 8337 6445 56 H(1AB) −3008 8283 6896 55 H(3AB) 1358 9452 7284 59 H(14A) −9307 9042 5399 58 H(4AA) 363 9843 6686 59 H(4AB) 2855 9400 6681 59 H(13A) −4349 9078 4977 51 H(7AA) −4044 8620 5914 60 H(17A) −9414 8836 4624 56 H(15A) −5210 8145 5369 59 H(15B) −8177 8093 5557 59 H(9AA) −8336 9998 5677 62 H(9AB) −5281 10140 5802 62 H(12A) −6487 9896 4689 55 H(12b) −9123 9821 4943 55 H(16A) −10428 8123 5010 60 H(16B) −7704 7797 4884 60 H(21A) −3850 9281 4334 72 H(21B) −6364 9194 4063 72 H(21C) −3535 8874 3988 72 H(20A) −4155 8293 4514 53 H(11A) −3707 10126 5198 61 H(11B) −6304 10539 5209 61 H(6AA) −2553 9730 6201 57 H(22A) −5981 7928 3955 82 H(22B) −8841 8235 4031 82 H(22C) −7870 7716 4282 82 H(1A′) 2123 7979 7458 114 H(2A′) 2789 8630 7600 114 H(3BA) −2777 10226 7889 72 H(1BA) −4248 11964 8280 60 H(1BB) −2397 11477 7816 47 H(10C) −7059 11915 7420 59 H(10D) −3958 12098 7346 59 H(3BB) −7298 10278 7744 55 H(4BA) −6208 10435 7105 57 H(4BB) −8532 10859 7249 57 H(6BA) −3190 10912 6723 61 H(7BA) −1379 12089 6870 69 H(1B′) −8841 10751 8268 84 H(2B′) −7733 11389 8381 84 H(12C) 1489 12288 5463 126 H(12D) 4012 12045 5691 126 H(9BA) −563 11014 6199 78 H(9BB) 2594 11184 6199 78 H(14B) 3687 12175 6372 79 H(13B) −381 12719 5970 103 H(11C) 1004 11288 5606 115 H(11D) −1538 11661 5737 115 H(15C) 2846 12767 6831 134 H(15D) −5 12972 6664 134 H(17B) 5058 13103 5913 131 H(16C) 2418 13724 6451 121 H(16D) 5278 13387 6482 121 H(20B) 220 13778 5830 181 H(22D) 3864 14386 5502 277 H(22E) 5760 14097 5804 277 H(22F) 3189 14475 5922 277 H(21D) −117 13593 5245 349 H(21E) 1547 13024 5339 349 H(21F) 3116 13572 5186 349 H(12E) 785 11834 5360 54 H(12F) 3241 11581 5598 54 H(9BC) 1963 10874 6148 55 H(9BD) −1223 10796 6237 55 H(14′) 4150 11946 6235 54 H(13′) −708 12386 5882 44 H(11E) −427 10915 5590 47 H(11F) −2464 11390 5746 47 H(15E) 3449 12658 6683 39 H(15F) 490 12824 6519 39 H(17′) 4716 12684 5669 45 H(16E) 5753 13064 6201 42 H(16F) 3094 13466 6185 42 H(20C) 240 13461 5697 87 H(22G) 2711 14036 5282 118 H(22H) 5163 13584 5286 118 H(22I) 4425 13933 5646 118 H(21G) −707 13362 5071 114 H(21H) −1382 12784 5285 114 H(21I) 1345 12832 5048 114 H(1A) −219 14814 6255 81 H(2A) −706 14251 6784 77 H(3A) 3213 13911 7091 83 H(4A) 7619 14134 6869 69 H(5A) 8105 14697 6340 75 H(6A) 4186 15037 6032 89

TABLE 7 Observed and calculated structure factors for 051810. h k l 10Fo 10Fc 10s h k l 10Fo 10Fc 10s h k l 10Fo 10Fc 10s h k l 10Fo 10Fc 10s h k l 10Fo 10Fc 10s 2 0 0 42 37 16 3 0 1 336 325 28 2 11 1 322 300 23 −3 1 2 263 203 23 2 11 2 356 337 16 4 0 0 138 110 15 4 0 1 0 25 1 3 11 1 63 25 49 −2 1 2 315 296 10 3 11 2 206 176 15 1 1 0 437 450 11 −3 1 1 201 154 25 −4 12 1 194 205 21 −1 1 2 1086 934 28 −4 12 2 92 98 42 2 1 0 362 322 16 −2 1 1 116 114 8 −3 12 1 232 275 22 0 1 2 752 671 17 −3 12 2 200 196 18 3 1 0 252 218 24 −1 1 1 1143 962 30 −2 12 1 284 258 14 1 1 2 1040 934 33 −2 12 2 178 157 9 0 2 0 271 282 8 0 1 1 134 157 3 −1 12 1 522 526 18 2 1 2 338 296 14 −1 12 2 294 255 15 1 2 0 426 437 14 1 1 1 1115 961 54 0 12 1 680 694 30 3 1 2 241 203 26 0 12 2 286 242 28 2 2 0 277 256 13 2 1 1 125 114 9 1 12 1 509 525 23 4 1 2 147 115 13 1 12 2 275 255 15 3 2 0 352 250 29 3 1 1 212 154 23 2 12 1 260 258 9 −4 2 2 0 44 1 2 12 2 167 157 9 4 2 0 158 155 27 4 1 1 159 141 16 3 12 1 285 275 14 −3 2 2 297 289 26 3 12 2 216 196 31 1 3 0 177 158 10 −3 2 1 441 430 24 4 12 1 198 205 20 −2 2 2 679 628 20 4 12 2 110 98 16 2 3 0 400 366 25 −2 2 1 436 399 19 −4 13 1 80 79 45 0 2 2 84 89 5 −4 13 2 161 165 22 3 3 0 502 441 19 −1 2 1 1871 1484 56 −2 13 1 91 91 13 2 2 2 663 627 43 −3 13 2 209 217 18 4 3 0 108 115 41 0 2 1 142 155 3 −1 13 1 164 146 11 3 2 2 299 289 25 −2 13 2 67 40 28 0 4 0 2471 1827 86 1 2 1 1819 1485 117 0 13 1 365 339 38 4 2 2 23 44 23 −1 13 2 136 167 32 1 4 0 364 399 10 2 2 1 432 400 28 1 13 1 152 147 10 −3 3 2 176 158 17 0 13 2 457 437 21 2 4 0 337 336 22 3 2 1 453 431 34 2 13 1 69 92 17 −2 3 2 554 530 24 1 13 2 173 167 12 3 4 0 262 232 10 4 2 1 117 84 36 3 13 1 292 333 16 −1 3 2 403 447 12 2 13 2 60 40 20 4 4 0 121 91 37 −3 3 1 95 101 19 4 13 1 80 79 19 0 3 2 207 208 5 3 13 2 221 217 20 1 5 0 76 86 7 −2 3 1 356 355 23 −4 14 1 132 123 26 1 3 2 400 446 11 4 13 2 166 164 11 2 5 0 79 85 29 −1 3 1 861 840 26 −3 14 1 56 95 55 2 3 2 481 530 37 −4 14 2 106 114 34 3 5 0 117 101 12 0 3 1 1901 1442 47 −2 14 1 247 228 11 3 3 2 153 158 7 −3 14 2 170 192 14 4 5 0 175 222 27 1 3 1 857 839 30 −1 14 1 83 79 16 4 3 2 62 50 62 −2 14 2 118 88 17 0 6 0 296 309 14 2 3 1 358 354 23 0 14 1 324 311 11 −3 4 2 300 241 11 −1 14 2 197 158 23 1 6 0 589 676 20 3 3 1 139 100 15 1 14 1 65 79 30 −2 4 2 218 219 11 0 14 2 66 57 26 2 6 0 86 46 29 4 3 1 89 72 57 2 14 1 261 227 9 −1 4 2 639 687 17 1 14 2 171 158 11 3 6 0 199 199 14 −4 4 1 146 157 30 3 14 1 77 94 31 0 4 2 122 154 5 2 14 2 81 89 16 1 7 0 111 130 6 −3 4 1 294 284 11 4 14 1 116 123 14 1 4 2 651 686 15 3 14 2 165 192 18 2 7 0 99 12 27 −2 4 1 334 364 20 −3 15 1 11 72 11 2 4 2 200 219 18 4 14 2 118 114 14 3 7 0 164 132 10 −1 4 1 415 464 11 −2 15 1 164 167 10 3 4 2 310 241 12 −3 15 2 92 86 21 0 8 0 833 923 65 0 4 1 961 903 26 −1 15 1 119 102 13 4 4 2 113 91 40 −2 15 2 201 183 9 1 8 0 272 335 26 1 4 1 415 464 10 0 15 1 62 54 23 −3 5 2 346 301 12 −1 15 2 122 96 13 2 8 0 75 86 41 2 4 1 308 364 22 1 15 1 88 103 19 −2 5 2 56 61 24 0 15 2 16 5 15 3 8 0 158 156 23 3 4 1 292 283 12 2 15 1 166 167 10 −1 5 2 761 787 25 1 15 2 125 97 13 1 9 0 300 305 18 4 4 1 154 156 28 3 15 1 0 72 1 0 5 2 393 436 12 2 15 2 197 182 13 2 9 0 293 277 14 −3 5 1 218 162 21 −3 16 1 106 124 20 1 5 2 744 787 20 3 15 2 71 87 41 3 9 0 306 302 16 −2 5 1 251 211 16 −2 16 1 98 95 14 2 5 2 0 61 1 −3 16 2 161 175 29 0 10 0 259 184 39 −1 5 1 621 673 26 −1 16 1 79 59 29 3 5 2 344 301 14 −2 16 2 117 99 12 1 10 0 259 210 11 0 5 1 143 120 6 0 16 1 40 1 40 4 5 2 110 82 42 −1 16 2 157 148 14 2 10 0 77 5 43 1 5 1 624 673 16 1 16 1 87 59 25 −3 6 2 175 123 10 0 16 2 64 71 21 3 10 0 97 83 21 2 5 1 214 212 19 2 16 1 88 94 17 −2 6 2 245 245 12 1 16 2 152 148 15 1 11 0 348 359 13 3 5 1 193 163 11 3 16 1 111 124 18 −1 6 2 194 197 18 2 16 2 108 100 14 2 11 0 86 11 31 4 5 1 97 32 53 −3 17 1 85 71 25 0 6 2 717 764 21 3 16 2 165 175 14 3 11 0 236 225 17 −3 6 1 286 246 11 −2 17 1 272 247 10 1 6 2 184 199 7 −3 17 2 85 87 25 4 11 0 288 303 23 −2 6 1 179 174 25 −1 17 1 162 152 15 2 6 2 252 246 18 −2 17 2 52 37 36 0 12 0 585 527 37 −1 6 1 187 202 12 0 17 1 76 18 18 3 6 2 154 123 12 −1 17 2 91 86 25 1 12 0 283 234 12 0 6 1 478 526 14 1 17 1 159 153 15 4 6 2 71 16 71 0 17 2 365 396 10 2 12 0 344 321 15 1 6 1 170 202 6 2 17 1 280 248 10 −3 7 2 204 172 11 1 17 2 87 86 26 3 12 0 88 37 25 2 6 1 172 175 18 3 17 1 85 71 18 −2 7 2 233 236 19 2 17 2 53 37 35 4 12 0 169 156 21 3 6 1 284 246 15 −3 18 1 96 80 16 −1 7 2 144 136 16 3 17 2 80 87 20 1 13 0 38 9 37 −3 7 1 122 113 11 −2 18 1 103 83 13 0 7 2 133 137 11 −3 18 2 46 47 45 2 13 0 97 124 22 −2 7 1 399 369 17 −1 18 1 147 118 15 1 7 2 123 135 6 −2 18 2 128 146 12 3 13 0 168 188 18 −1 7 1 317 373 10 0 18 1 236 218 10 2 7 2 224 236 20 −1 18 2 161 73 48 4 13 0 88 4 40 0 7 1 185 170 7 1 18 1 119 118 24 3 7 2 201 172 10 0 18 2 153 126 16 0 14 0 105 104 19 1 7 1 313 372 9 2 18 1 66 83 22 4 7 2 141 21 25 1 18 2 74 73 35 1 14 0 164 161 11 2 7 1 368 369 28 3 18 1 46 80 46 −4 8 2 97 21 38 2 18 2 156 145 13 2 14 0 123 93 11 3 7 1 128 112 17 −3 19 1 75 77 21 −3 8 2 215 196 10 3 18 2 51 46 50 3 14 0 89 139 27 4 7 1 146 100 24 −2 19 1 115 124 11 −2 8 2 211 197 12 −3 19 2 20 9 20 4 14 0 0 50 1 −3 8 1 116 91 14 −1 19 1 103 120 19 −1 8 2 194 171 15 −2 19 2 157 149 18 1 15 0 83 60 30 −2 8 1 104 93 13 0 19 1 175 179 11 0 8 2 561 743 24 −1 19 2 143 167 14 2 15 0 248 227 10 −1 8 1 196 223 11 1 19 1 75 120 28 1 8 2 163 171 12 0 19 2 109 68 20 3 15 0 283 273 15 0 8 1 115 77 14 2 19 1 118 124 11 2 8 2 217 196 19 1 19 2 119 167 16 0 16 0 77 26 25 1 8 1 194 222 13 3 19 1 49 77 48 3 8 2 203 197 10 2 19 2 160 149 17 1 16 0 40 24 40 2 8 1 107 92 12 −2 20 1 215 209 11 4 8 2 110 22 32 3 19 2 55 9 41 2 16 0 63 39 23 3 8 1 135 91 12 −1 20 1 64 54 32 −3 9 2 160 150 24 −2 20 2 98 96 13 3 16 0 62 93 61 4 8 1 101 62 36 0 20 1 69 84 27 −3 9 2 183 181 12 −1 20 2 0 92 1 1 17 0 50 8 50 −3 9 1 114 91 17 1 20 1 0 54 1 −2 9 2 248 217 12 0 20 2 71 19 42 2 17 0 58 46 57 −2 9 1 122 115 16 2 20 1 207 209 14 −1 9 2 146 110 18 1 20 2 45 93 45 3 17 0 114 143 14 −1 9 1 522 569 22 −2 21 1 0 24 1 0 9 2 352 351 13 2 20 2 104 96 28 0 18 0 100 100 25 0 9 1 556 610 16 −1 21 1 77 97 21 1 9 2 136 111 15 −2 21 2 112 116 19 1 18 0 122 122 27 1 9 1 513 570 22 0 21 1 155 180 11 2 9 2 243 217 13 −1 21 2 0 31 1 2 18 0 65 44 29 2 9 1 126 116 11 1 21 1 83 97 19 3 9 2 185 180 13 0 21 2 64 29 31 3 18 0 67 21 37 3 9 1 79 92 30 2 21 1 42 25 42 4 9 2 172 150 21 1 21 2 0 31 1 1 19 0 67 82 34 −4 10 1 132 78 27 −1 22 1 72 95 22 −4 10 2 93 53 39 2 21 2 127 116 17 2 19 0 86 77 15 −3 10 1 195 194 19 0 22 1 130 155 15 −3 10 2 137 102 14 −2 22 2 93 47 38 3 19 0 44 9 43 −2 10 1 262 248 10 1 22 1 54 95 54 −2 10 2 97 72 16 −1 22 2 50 67 43 0 20 0 188 199 19 −1 10 1 375 400 14 2 22 1 0 55 1 −1 10 2 77 76 17 0 22 2 171 153 11 1 20 0 0 42 1 0 10 1 690 690 21 −1 23 1 120 133 12 0 10 2 950 934 28 1 22 2 40 67 40 2 20 0 154 143 15 1 10 1 375 401 14 0 23 1 100 89 17 1 10 2 87 77 14 −1 23 2 73 67 20 1 21 0 54 48 41 2 10 1 264 247 10 1 23 1 93 133 21 2 10 2 70 71 35 0 23 2 56 89 56 2 21 0 138 110 30 3 10 1 197 193 13 0 24 1 73 28 65 3 10 2 112 103 19 1 23 2 77 68 23 0 22 0 127 96 19 −4 11 1 35 51 35 0 0 2 730 648 22 −4 11 2 118 83 30 1 0 3 1331 1063 37 1 22 0 46 3 46 −3 11 1 50 25 50 1 0 2 696 652 18 −3 11 2 200 176 15 2 0 3 191 167 10 2 22 0 0 4 1 −2 11 1 328 299 17 2 0 2 545 482 23 −2 11 2 351 337 11 3 0 3 0 15 1 1 23 0 56 47 55 −1 11 1 242 239 11 3 0 2 143 121 29 −1 11 2 276 254 11 4 0 3 61 39 38 1 0 1 273 277 9 0 11 1 128 104 10 4 0 2 158 104 14 0 11 2 223 180 12 −4 1 3 113 112 17 2 0 1 277 257 12 1 11 1 247 240 10 −4 1 2 120 115 17 1 11 2 258 253 11 −3 1 3 63 76 63 −2 1 3 883 766 31 −3 11 3 156 130 16 0 0 4 609 605 21 −2 10 4 196 193 10 2 21 4 55 99 54 0 1 3 237 298 5 −2 11 3 131 124 8 1 0 4 1364 1149 59 −1 10 4 241 225 11 −2 22 4 79 106 78 1 1 3 2688 1939 125 −1 11 3 353 357 14 2 0 4 258 251 18 0 10 4 181 202 9 −1 22 4 0 34 1 2 1 3 881 767 54 0 11 3 308 330 12 3 0 4 124 63 36 1 10 4 247 224 10 0 22 4 60 3 43 3 1 3 55 76 55 1 11 3 368 355 13 4 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24 112 111 13 2 13 21 108 116 15 1 7 22 263 266 10 3 2 23 7 52 7 −1 16 23 40 30 40 −1 11 24 112 117 14 3 13 21 73 61 21 2 7 22 131 135 13 −3 3 23 96 95 16 0 16 23 122 142 16 0 11 24 212 204 15 −2 14 21 90 78 15 3 7 22 21 20 20 −2 3 23 59 76 34 1 16 23 76 30 37 1 11 24 125 118 25 −1 14 21 78 75 20 −3 8 22 99 103 15 −1 3 23 61 66 29 2 16 23 119 94 17 2 11 24 80 111 33 0 14 21 41 87 40 −2 8 22 47 40 46 0 3 23 294 260 13 −1 17 23 79 107 17 3 11 24 67 7 23 1 14 21 65 75 29 −1 8 22 171 139 9 1 3 23 92 65 17 0 17 23 57 42 56 −2 12 24 63 58 26 2 14 21 98 78 21 0 8 22 163 159 20 2 3 23 91 77 13 1 17 23 93 107 24 −1 12 24 126 81 23 −2 15 21 93 67 15 1 8 22 150 138 13 3 3 23 108 94 12 −1 18 23 0 9 1 0 12 24 54 74 53 −1 15 21 71 71 22 2 8 22 68 40 28 −3 4 23 52 16 45 0 18 23 30 54 29 1 12 24 109 80 15 0 15 21 106 118 20 3 8 22 77 104 16 −2 4 23 173 156 10 1 18 23 0 9 1 2 12 24 60 58 59 1 15 21 73 71 40 −3 9 22 110 104 23 −1 4 23 99 83 34 0 19 23 0 75 1 −2 13 24 124 130 12 2 15 21 89 67 88 −2 9 22 200 176 10 0 4 23 122 124 9 0 0 24 115 82 27 −1 13 24 275 287 9 −2 16 21 76 71 37 −1 9 22 99 103 17 1 4 23 104 83 13 1 0 24 315 301 13 0 13 24 70 57 46 −1 16 21 65 84 24 0 9 22 112 95 17 2 4 23 149 156 12 2 0 24 128 110 10 1 13 24 266 287 34 0 16 21 22 46 21 1 9 22 130 102 13 3 4 23 0 16 1 3 0 24 32 69 31 2 13 24 141 130 15 1 16 21 94 84 19 2 9 22 163 176 13 −3 5 23 61 66 29 −3 1 24 68 70 23 −2 14 24 48 16 47 2 16 21 83 70 27 3 9 22 93 103 15 −2 5 23 164 165 9 −2 1 24 237 215 11 −1 14 24 152 138 17 −2 17 21 90 78 16 −3 10 22 218 222 13 −1 5 23 219 183 16 −1 1 24 171 84 58 0 14 24 42 46 42 −1 17 21 95 112 14 −2 10 22 205 206 11 0 5 23 64 76 20 0 1 24 31 37 30 1 14 24 137 138 20 0 17 21 76 38 27 −1 10 22 58 34 36 1 5 23 205 182 9 1 1 24 114 84 13 2 14 24 78 16 30 1 17 21 129 112 18 0 10 22 63 25 62 2 5 23 156 164 12 2 1 24 230 216 11 −2 15 24 105 91 18 2 17 21 113 78 22 1 10 22 57 35 56 3 5 23 60 66 24 3 1 24 38 70 37 −1 15 24 167 203 11 −1 18 21 73 61 19 2 10 22 166 206 12 −3 6 23 82 69 19 −3 2 24 82 70 19 0 15 24 218 194 14 0 18 21 53 20 52 3 10 22 168 222 15 −2 6 23 122 111 12 −2 2 24 271 286 10 1 15 24 222 203 14 1 18 21 46 61 45 −3 11 22 186 172 14 −1 6 23 134 123 11 −1 2 24 119 115 28 2 15 24 131 91 16 −1 19 21 25 17 24 −2 11 22 181 191 12 0 6 23 318 291 9 0 2 24 49 4 32 −2 16 24 81 27 80 0 19 21 135 143 18 −1 11 22 235 228 10 1 6 23 133 123 11 1 2 24 125 116 14 −1 16 24 61 75 44 1 19 21 50 17 49 0 11 22 367 323 19 2 6 23 105 111 17 2 2 24 271 287 14 0 16 24 0 18 1 0 20 21 109 48 28 1 11 22 253 228 11 3 6 23 48 70 47 3 2 24 73 70 18 1 16 24 74 75 34 0 0 22 390 413 19 2 11 22 170 190 15 −3 7 23 45 16 45 −3 3 24 0 47 1 −1 17 24 104 98 13 1 0 22 41 23 40 3 11 22 146 172 12 −2 7 23 118 122 12 −2 3 24 80 37 21 0 17 24 36 57 35 2 0 22 230 213 10 −3 12 22 38 64 37 −1 7 23 162 146 9 −1 3 24 344 300 20 1 17 24 87 99 24 3 0 22 210 222 23 −2 12 22 80 66 18 0 7 23 63 48 26 0 3 24 89 73 13 −1 18 24 54 56 53 4 0 22 72 84 71 −1 12 22 81 94 20 1 7 23 161 145 14 1 3 24 324 300 12 0 18 24 0 52 1 −4 1 22 94 67 20 0 12 22 14 50 13 2 7 23 120 122 14 2 3 24 27 37 26 1 0 25 122 111 15 −3 1 22 140 162 63 1 12 22 127 95 14 3 7 23 0 16 1 3 3 24 41 47 41 2 0 25 82 34 18 −2 1 22 129 128 10 2 12 22 57 66 36 −3 8 23 78 53 28 −3 4 24 71 70 24 3 0 25 200 195 17 −1 1 22 132 125 10 3 12 22 56 64 31 −2 8 23 63 22 24 −2 4 24 134 124 11 −3 1 25 105 95 14 0 1 22 273 267 13 −3 13 22 62 73 21 −1 8 23 51 37 51 −1 4 24 0 29 1 −2 1 25 202 164 9 1 1 22 111 126 20 −2 13 22 126 163 12 0 8 23 153 138 12 0 4 24 283 280 8 −1 1 25 96 78 21 2 1 22 135 128 9 −1 13 22 227 225 9 1 8 23 90 37 19 1 4 24 66 28 25 0 1 25 98 111 13 3 1 22 141 162 11 0 13 22 88 80 25 2 8 23 45 22 44 2 4 24 136 124 10 1 1 25 103 78 27 2 1 25 179 164 18 0 15 25 86 64 32 2 11 26 103 99 20 2 9 27 135 153 19 2 8 28 97 78 17 3 1 25 100 95 16 1 15 25 150 162 18 −2 12 26 79 78 20 −2 10 27 51 59 51 −2 9 28 55 73 39 −3 2 25 0 9 1 2 15 25 30 21 29 −1 12 26 158 164 10 −1 10 27 167 139 13 −1 9 28 46 54 45 −2 2 25 60 14 50 −1 16 25 31 46 31 0 12 26 124 120 19 0 10 27 54 60 53 0 9 28 0 33 1 −1 2 25 227 206 13 0 16 25 148 190 22 1 12 26 166 164 14 1 10 27 128 140 18 1 9 28 56 55 56 0 2 25 61 36 21 1 16 25 59 45 58 2 12 26 107 78 23 2 10 27 86 59 23 2 9 28 99 73 16 1 2 25 224 206 14 −1 17 25 61 49 24 −2 13 26 110 97 14 −2 11 27 49 69 49 −2 10 28 74 81 21 2 2 25 45 14 45 0 17 25 0 30 1 −1 13 26 0 35 1 −1 11 27 106 106 14 −1 10 28 76 34 22 3 2 25 47 10 47 1 17 25 30 49 29 0 13 26 101 111 22 0 11 27 52 92 52 0 10 28 95 97 27 −3 3 25 45 39 44 0 18 25 0 22 1 1 13 26 37 35 37 1 11 27 110 105 26 1 10 28 50 35 50 −2 3 25 101 65 15 0 0 26 167 153 14 2 13 26 115 97 18 2 11 27 84 68 26 2 10 28 72 81 33 −1 3 25 91 91 31 1 0 26 101 36 24 −2 14 26 28 34 27 −2 12 27 86 125 36 −2 11 28 61 48 30 0 3 25 70 5 18 2 0 26 146 116 15 −1 14 26 43 39 43 −1 12 27 94 111 16 −1 11 28 95 101 28 1 3 25 110 92 21 3 0 26 78 35 67 0 14 26 92 47 25 0 12 27 59 6 59 0 11 28 194 168 50 2 3 25 51 65 36 −3 1 26 56 48 29 1 14 26 30 39 29 1 12 27 108 110 19 1 11 28 64 100 41 3 3 25 0 38 1 −2 1 26 76 80 20 2 14 26 0 35 1 2 12 27 119 125 17 2 11 28 46 48 46 −3 4 25 84 90 33 −1 1 26 79 43 35 −1 15 26 74 57 19 −2 13 27 0 53 1 −2 12 28 45 20 44 −2 4 25 57 44 31 0 1 26 324 319 10 0 15 26 132 124 17 −1 13 27 0 35 1 −1 12 28 60 35 30 −1 4 25 185 172 15 1 1 26 82 43 40 1 15 26 69 57 38 0 13 27 197 213 15 0 12 28 167 159 16 0 4 25 272 278 9 2 1 26 91 81 15 −1 16 26 0 51 1 1 13 27 54 36 53 1 12 28 67 36 48 1 4 25 175 172 12 3 1 26 46 49 46 0 16 26 58 66 58 2 13 27 78 53 77 2 12 28 0 20 1 2 4 25 54 45 27 −3 2 26 119 132 13 1 16 26 53 51 52 −1 14 27 56 65 31 −2 13 28 52 66 52 3 4 25 85 90 15 −2 2 26 141 132 12 0 17 26 0 17 1 0 14 27 60 31 60 −1 13 28 114 133 13 −3 5 25 0 11 1 −1 2 26 159 105 15 1 0 27 104 67 24 1 14 27 0 65 1 0 13 28 57 7 57 −2 5 25 118 114 12 0 2 26 146 129 10 2 0 27 198 166 13 −1 15 27 91 76 15 1 13 28 99 133 24 −1 5 25 83 101 31 1 2 26 126 104 20 3 0 27 74 56 19 0 15 27 52 17 52 −1 14 28 84 55 18 0 5 25 171 175 9 2 2 26 141 132 13 −3 1 27 124 125 12 1 15 27 78 76 28 0 14 28 68 67 43 1 5 25 89 101 24 3 2 26 117 133 11 −2 1 27 135 127 11 −1 16 27 28 22 27 1 14 28 63 55 45 2 5 25 135 114 13 −3 3 26 81 51 19 −1 1 27 124 129 20 0 16 27 110 119 27 −1 15 28 130 131 12 3 5 25 32 11 32 −2 3 26 68 79 22 0 1 27 136 123 11 1 16 27 38 23 38 0 15 28 0 25 1 −3 6 25 101 68 24 −1 3 26 120 91 22 1 1 27 142 129 18 0 0 28 376 331 19 1 15 28 117 132 17 −2 6 25 146 155 10 0 3 26 82 51 15 2 1 27 155 127 18 1 0 28 132 99 21 0 16 28 0 31 1 −1 6 25 104 89 20 1 3 26 125 91 21 3 1 27 141 125 12 2 0 28 49 36 49 1 0 29 227 220 29 0 6 25 107 83 16 2 3 26 80 79 16 −3 2 27 103 106 13 3 0 28 71 71 19 2 0 29 87 76 15 1 6 25 122 88 14 3 3 26 0 51 1 −2 2 27 106 87 15 −3 1 28 102 106 13 3 0 29 59 59 26 2 6 25 128 154 14 −3 4 26 146 112 20 −1 2 27 79 66 36 −2 1 28 97 67 24 −3 1 29 52 54 51 3 6 25 77 69 17 −2 4 26 102 64 13 0 2 27 126 122 13 −1 1 28 175 128 15 −2 1 29 135 139 24 −3 7 25 151 150 11 −1 4 26 181 168 15 1 2 27 92 66 27 0 1 28 50 17 50 −1 1 29 110 51 20 −2 7 25 136 111 12 0 4 26 78 62 26 2 2 27 107 87 14 1 1 28 130 128 20 0 1 29 37 28 36 −1 7 25 89 41 24 1 4 26 161 168 16 3 2 27 112 107 14 2 1 28 69 67 21 1 1 29 74 51 36 0 7 25 46 66 46 2 4 26 61 64 22 −3 3 27 168 152 15 3 1 28 132 106 12 2 1 29 124 140 10 1 7 25 96 42 35 3 4 26 107 113 13 −2 3 27 135 139 11 −3 2 28 108 116 13 3 1 29 87 54 20 2 7 25 127 111 14 −3 5 26 84 69 18 −1 3 27 229 239 14 −2 2 28 118 118 12 −3 2 29 109 104 12 3 7 25 130 150 10 −2 5 26 166 151 10 0 3 27 98 100 27 −1 2 28 129 127 31 −2 2 29 126 88 14 −3 8 25 49 60 49 −1 5 26 109 42 23 1 3 27 226 240 30 0 2 28 70 11 27 −1 2 29 301 291 33 −2 8 25 104 91 15 0 5 26 13 5 13 2 3 27 116 140 13 1 2 28 151 126 16 0 2 29 120 99 17 −1 8 25 191 203 11 1 5 26 86 42 32 3 3 27 143 151 11 2 2 28 107 117 12 1 2 29 252 291 26 0 8 25 26 43 26 2 5 26 151 150 17 −3 4 27 66 56 25 3 2 28 139 117 12 2 2 29 90 88 13 1 8 25 200 202 15 3 5 26 70 69 20 −2 4 27 110 112 15 −3 3 28 73 42 18 3 2 29 126 104 14 2 8 25 101 91 16 −3 6 26 70 26 22 −1 4 27 49 43 49 −2 3 28 184 168 13 −3 3 29 114 124 12 3 8 25 80 59 18 −2 6 26 0 31 1 0 4 27 310 274 12 −1 3 28 112 84 40 −2 3 29 70 42 27 −3 9 25 0 35 1 −1 6 26 195 185 15 1 4 27 0 43 1 0 3 28 118 105 15 −1 3 29 62 38 61 −2 9 25 20 45 20 0 6 26 127 131 14 2 4 27 133 113 19 1 3 28 103 83 22 0 3 29 297 282 11 −1 9 25 200 188 10 1 6 26 183 184 15 3 4 27 63 56 24 2 3 28 175 168 14 1 3 29 55 39 55 0 9 25 153 164 26 2 6 26 6 31 5 −3 5 27 0 41 1 3 3 28 44 42 43 2 3 29 0 41 1 1 9 25 208 188 21 3 6 26 0 26 1 −2 5 27 102 67 18 −3 4 28 179 161 10 3 3 29 113 124 15 2 9 25 65 44 29 −3 7 26 39 25 38 −1 5 27 191 175 16 −2 4 28 106 119 21 −3 4 29 50 73 50 3 9 25 72 34 71 −2 7 26 86 59 19 0 5 27 69 18 29 −1 4 28 150 182 17 −2 4 29 53 60 53 −3 10 25 68 73 34 −1 7 26 189 165 12 1 5 27 192 174 32 0 4 28 459 389 15 −1 4 29 94 90 25 −2 10 25 24 37 23 0 7 26 51 25 50 2 5 27 64 67 62 1 4 28 168 182 14 0 4 29 84 62 22 −1 10 25 132 115 12 1 7 26 167 165 16 3 5 27 16 41 16 2 4 28 157 119 23 1 4 29 113 90 18 0 10 25 101 79 27 2 7 26 86 60 19 −3 6 27 51 36 50 3 4 28 158 161 12 2 4 29 70 59 24 1 10 25 114 116 54 3 7 26 0 25 1 −2 6 27 176 182 12 −3 5 28 0 21 1 3 4 29 82 73 17 2 10 25 81 37 20 −3 8 26 87 75 17 −1 6 27 130 91 24 −2 5 28 123 125 14 −3 5 29 105 108 15 3 10 25 75 73 20 −2 8 26 77 25 22 0 6 27 387 341 13 −1 5 28 79 31 38 −2 5 29 173 154 17 −2 11 25 176 147 10 −1 8 26 46 39 46 1 6 27 99 90 24 0 5 28 375 314 13 −1 5 29 238 233 25 −1 11 25 334 282 10 0 8 25 72 52 32 2 6 27 175 182 15 1 5 28 0 31 1 0 5 29 46 23 46 0 11 25 92 85 30 1 8 26 0 40 1 3 6 27 53 36 39 2 5 28 142 125 17 1 5 29 215 234 14 1 11 25 289 282 19 2 8 26 40 25 39 −3 7 27 51 32 51 3 5 28 58 21 28 2 5 29 128 154 18 2 11 25 137 147 16 3 8 26 97 74 15 −2 7 27 68 21 25 −3 6 28 0 50 1 3 5 29 81 108 22 −2 12 25 129 139 14 −3 9 26 131 76 15 −1 7 27 183 175 10 −2 6 28 68 76 26 −2 6 29 0 24 1 −1 12 25 119 110 12 −2 9 26 61 80 30 0 7 27 265 251 12 −1 6 28 268 259 13 −1 6 29 0 44 1 0 12 25 132 113 20 −1 9 26 153 127 11 1 7 27 160 174 16 0 6 28 69 25 28 0 6 29 129 150 15 1 12 25 109 111 49 0 9 26 112 70 18 2 7 27 21 21 21 1 6 23 225 259 18 1 6 29 0 43 1 2 12 25 156 139 14 1 9 26 122 127 27 3 7 27 31 32 30 2 6 28 53 76 53 2 6 29 61 24 56 −2 13 25 177 187 11 2 9 26 116 80 19 −3 8 27 53 49 53 3 6 28 55 50 55 −2 7 29 69 52 29 −1 13 25 78 77 20 3 9 26 110 76 13 −2 8 27 200 206 10 −3 7 28 89 96 22 −1 7 29 66 50 32 0 13 25 222 210 28 −3 10 26 114 34 42 −1 8 27 217 209 10 −2 7 28 136 124 12 0 7 29 189 159 12 1 13 25 64 77 64 −2 10 26 127 101 23 0 8 27 74 58 29 −1 7 28 165 141 15 1 7 29 0 50 1 2 13 25 198 188 13 −1 10 26 99 71 21 1 8 27 202 209 15 0 7 28 89 71 40 2 7 29 62 52 30 −2 14 25 43 45 42 0 10 26 107 117 25 2 8 27 218 207 28 1 7 28 116 141 19 −2 8 29 53 59 53 −1 14 25 179 177 9 1 10 26 100 72 23 3 8 27 57 50 48 2 7 28 95 124 20 −1 8 29 45 16 45 0 14 25 244 266 15 2 10 26 107 101 16 −3 9 27 0 69 1 3 7 28 83 96 28 0 8 29 87 59 33 1 14 25 184 176 17 −2 11 26 84 99 19 −2 9 27 139 153 11 −2 8 28 96 78 23 1 8 29 53 16 52 2 14 25 0 44 1 −1 11 26 169 176 13 −1 9 27 114 126 14 −1 8 28 133 111 12 2 8 29 54 60 53 −2 15 25 39 22 39 0 11 26 63 119 62 0 9 27 194 140 15 0 8 28 67 55 35 −2 9 29 68 24 25 −1 15 25 178 162 9 1 11 26 167 176 29 1 9 27 117 126 28 1 6 28 133 111 17 −1 9 29 17 2 17 0 9 29 95 67 19 −1 8 30 104 96 26 −1 9 31 96 99 15 1 0 33 154 164 15 1 5 34 111 115 19 1 9 29 0 2 1 0 8 30 126 95 18 0 9 31 71 30 37 2 0 33 84 33 27 −1 6 34 63 61 28 2 9 29 0 24 1 1 8 30 75 96 35 1 9 31 126 98 16 −2 1 33 122 104 20 0 6 34 0 17 1 −2 10 29 46 46 45 2 8 30 83 133 51 2 9 31 115 71 33 −1 1 33 109 108 18 1 6 34 107 62 20 −1 10 29 161 167 10 −2 9 30 0 51 1 −1 10 31 63 62 28 0 1 33 163 152 11 −1 7 34 60 72 36 0 10 29 79 35 22 −1 9 30 135 129 18 0 10 31 87 85 20 1 1 33 92 108 23 0 7 34 37 52 37 1 10 29 163 167 61 0 9 30 206 209 16 1 10 31 84 62 25 2 1 33 82 104 40 1 7 34 61 73 61 2 10 29 0 46 1 1 9 30 144 129 40 −1 11 31 54 62 37 −2 2 33 97 78 15 −1 8 34 0 37 1 −2 11 29 96 55 16 2 9 30 83 51 61 0 11 31 0 43 1 −1 2 33 77 115 26 0 8 34 100 86 17 −1 11 29 97 79 15 −2 10 30 30 20 29 1 11 31 78 62 32 0 2 33 143 129 14 1 8 34 73 37 32 0 11 29 143 97 17 −1 10 30 142 136 11 −1 12 31 15 13 14 1 2 33 86 114 25 −1 9 34 81 62 21 1 11 29 82 79 26 0 10 30 14 24 14 0 12 31 0 33 1 2 2 33 75 79 50 0 9 34 0 42 1 2 11 29 0 54 1 1 10 30 129 137 17 1 12 31 0 14 1 −2 3 33 0 33 1 1 9 34 78 62 33 −2 12 29 46 42 46 2 10 30 76 20 75 −1 13 31 92 107 32 −1 3 33 69 31 31 0 10 34 83 63 27 −1 12 29 17 49 16 −2 11 30 50 33 50 0 13 31 41 17 40 0 3 33 188 199 11 1 0 35 0 6 1 0 12 29 227 193 18 −1 11 30 65 59 26 0 0 32 185 180 18 1 3 33 71 31 44 −1 1 35 61 24 54 1 12 29 0 49 1 0 11 30 39 7 39 1 0 32 139 166 15 2 3 33 55 33 55 0 1 35 89 39 25 −1 13 29 47 66 47 1 11 30 75 60 36 2 0 32 46 38 45 −2 4 33 92 73 19 1 1 35 62 24 45 0 13 29 0 42 1 −1 12 30 46 54 45 −2 1 32 128 126 12 −1 4 33 112 140 14 −1 2 35 75 63 74 1 13 29 81 66 28 0 12 30 34 25 34 −1 1 32 92 124 21 0 4 33 78 75 24 0 2 35 0 71 1 −1 14 29 97 92 21 1 12 30 40 55 40 0 1 32 105 106 17 1 4 33 148 139 23 1 2 35 106 63 21 0 14 29 55 26 54 −1 13 30 72 88 34 1 1 32 98 124 21 2 4 33 27 74 26 −1 3 35 0 30 1 1 14 29 92 92 21 0 13 30 0 4 1 2 1 32 125 126 24 −2 5 33 02 76 19 0 35 96 80 20 0 15 29 0 30 1 1 13 30 69 87 33 −2 2 32 77 79 25 −1 5 33 120 120 17 1 3 35 0 30 1 0 0 30 95 91 28 −1 14 30 85 87 33 −1 2 32 63 50 39 0 5 33 80 57 23 −1 4 35 89 93 19 1 0 30 12 14 12 0 14 30 33 10 33 0 2 32 93 84 19 1 5 33 133 121 17 0 4 35 0 18 1 2 0 30 144 143 13 1 0 31 23 11 23 1 2 32 69 50 36 2 5 33 77 76 77 1 4 35 109 93 21 3 0 30 104 93 16 2 0 31 128 146 14 2 2 32 62 79 61 −2 6 33 20 19 19 −1 5 35 46 50 45 −3 1 30 70 70 27 −2 1 31 123 115 15 −2 3 32 181 163 11 −1 6 33 0 42 1 0 5 35 0 6 1 −2 1 30 71 120 70 −1 1 31 159 177 28 −1 3 32 66 70 36 0 6 33 65 61 32 1 5 35 27 49 26 −1 1 30 203 200 32 0 1 31 187 200 15 0 3 32 34 39 34 1 6 33 55 42 54 −1 6 35 107 115 16 0 1 30 54 39 54 1 1 31 173 177 21 1 3 32 77 70 30 2 6 33 0 20 1 0 6 35 70 54 27 1 1 30 182 200 38 2 1 31 108 116 15 2 3 32 121 163 30 −1 7 33 111 112 14 1 6 35 126 115 17 2 1 30 126 120 12 −2 2 31 72 95 24 −2 4 32 81 70 21 0 7 33 69 44 29 −1 7 35 0 56 1 3 1 30 53 70 53 −1 2 31 0 79 1 −1 4 32 225 263 11 1 7 33 137 111 18 0 7 35 77 84 24 −3 2 30 49 33 48 0 2 31 25 15 24 0 4 32 96 98 20 −1 8 33 62 73 33 1 7 35 48 56 48 −2 2 30 37 64 36 1 2 31 87 79 24 1 4 32 219 263 14 0 8 33 6 18 5 −1 8 35 80 26 38 −1 2 30 143 136 23 2 2 31 56 94 55 2 4 32 89 71 24 1 8 33 82 74 27 0 8 35 46 50 46 0 2 30 146 144 12 −2 3 31 165 165 18 −2 5 32 42 55 41 −1 9 33 69 70 27 0 9 35 0 7 1 1 2 30 106 136 20 −1 3 31 71 87 32 −1 5 32 96 113 19 0 9 33 63 27 63 0 0 36 97 106 35 2 2 30 63 64 23 0 3 31 103 113 20 0 5 32 138 131 14 1 9 33 0 70 1 1 0 36 55 1 55 3 2 30 52 33 51 1 3 31 88 86 31 1 5 32 104 113 45 −1 10 33 8 50 8 −1 1 36 23 76 22 −3 3 30 0 21 1 2 3 31 117 166 19 2 5 32 0 55 1 0 10 33 48 11 48 0 1 36 28 24 28 −2 3 30 54 63 49 −2 4 31 126 122 13 −2 6 32 61 30 32 1 10 33 46 50 45 1 1 36 0 76 1 −1 3 30 57 68 56 −1 4 31 69 68 36 −1 6 32 134 146 12 0 11 33 132 125 13 −1 2 36 0 26 1 0 3 30 300 302 11 0 4 31 103 87 18 0 6 32 96 116 17 0 0 34 254 258 25 0 2 36 49 87 48 1 3 30 43 68 43 1 4 31 100 69 20 1 6 32 145 146 15 1 0 34 57 41 56 1 2 36 41 25 40 2 3 30 0 63 1 2 4 31 110 122 19 2 6 32 0 30 1 2 0 34 0 45 1 −1 3 36 56 32 47 −2 4 30 134 121 16 −2 5 31 109 93 15 −2 7 32 49 23 49 −2 1 34 51 20 50 0 3 36 84 38 25 −1 4 30 99 113 27 −1 5 31 159 179 32 −1 7 32 99 115 18 −1 1 34 120 141 17 1 3 36 0 32 1 0 4 30 229 206 10 0 5 31 0 25 1 0 7 32 106 82 52 0 1 34 150 131 13 −1 4 36 78 49 29 1 4 30 98 113 19 1 5 31 167 178 14 1 7 32 115 115 17 1 1 34 131 141 17 0 4 36 23 16 23 2 4 30 85 121 29 2 5 31 0 93 1 2 7 32 0 23 1 2 1 34 33 20 32 1 4 36 0 49 1 −2 5 30 110 114 17 −2 6 31 140 145 13 −2 8 32 50 83 49 −2 2 34 84 76 26 −1 5 36 55 40 55 −1 5 30 78 81 22 −1 6 31 80 33 21 −1 8 32 81 91 21 −1 2 34 92 103 21 0 5 36 44 40 43 0 5 30 125 120 14 0 6 31 167 181 12 0 8 32 70 38 28 0 2 34 123 120 15 1 5 36 51 40 51 1 5 30 52 81 52 1 6 31 42 33 41 1 8 32 82 90 28 1 2 34 103 103 20 0 6 36 85 58 23 2 5 30 105 114 20 2 6 31 151 145 34 2 8 32 112 83 33 2 2 34 0 76 1 0 7 36 88 105 22 −2 6 30 135 142 13 −2 7 31 78 57 22 −1 9 32 36 39 35 −2 3 34 51 39 50 1 0 37 87 62 26 −1 6 30 109 121 15 −1 7 31 77 100 48 0 9 32 50 68 50 −1 3 34 95 103 17 −1 1 37 75 69 62 0 6 30 47 48 47 0 7 31 142 140 12 1 9 32 65 39 42 0 3 34 161 176 24 0 1 37 68 67 37 1 6 30 111 121 18 1 7 31 86 99 34 −1 10 32 60 63 29 1 3 34 101 103 21 1 1 37 82 69 35 2 6 30 121 142 33 2 7 31 0 57 1 0 10 32 25 31 24 2 3 34 0 39 1 −1 2 37 24 56 24 −2 7 30 63 54 33 −2 8 31 0 37 1 1 10 32 63 63 63 −2 4 34 42 45 42 0 2 37 13 29 12 −1 7 30 70 95 23 −1 8 31 88 88 20 −1 11 32 80 66 19 −1 4 34 107 135 15 0 3 37 121 103 17 0 7 30 70 45 30 0 8 31 74 23 27 0 11 32 0 42 1 0 4 34 75 89 37 0 4 37 167 153 13 1 7 30 77 95 28 1 8 31 100 88 70 1 11 32 19 66 19 1 4 34 130 135 34 0 5 37 48 60 47 2 7 30 64 54 44 2 8 31 0 37 1 −1 12 32 0 42 1 −1 5 34 115 116 14 −2 8 30 130 134 14 −2 9 31 83 71 22 0 12 32 55 87 54 0 5 34 0 4 1

EXAMPLE 2 Synthesis of 051810

The preparation of 051810 having the basic structure I can be accomplished by a common general method, i.e. the condensation of a bicyclic Windaus-Grundmann type ketone II with the allylic phosphine oxide III to the corresponding 2-methylene-19-nor-vitamin D analog IV followed by deprotection at C-1 and C-3 in the latter compound IV to obtain compound I, i.e. 051810.

In phosphine oxide III, Y₁ and Y₂ are preferably hydroxy-protecting groups such as silyl protecting groups. The t-butyldimethylsilyl (TMDMS) group is an example of a particularly useful hydroxy-protecting group. The process described above represents an application of the convergent synthesis concept, which has been applied effectively to the preparation of numerous vitamin D compounds (see Lythgoe et al., J. Chem. Soc. Perkin Trans. I, 590 (1978); Lythgoe, Chem. Soc. Rev. 9, 449 (1983); Toh et al., J. Org. Chem. 48, 1414 (1983); Baggiolini et al., J. Org. Chem. 51, 3098 (1986); Sardina et al., J. Org. Chem. 51, 1264 (1986); J. Org. Chem. 51, 1269 (1986); DeLuca et al., U.S. Pat. No. 5,086,191; DeLuca et al., U.S. Pat. No. 5,536,713; and DeLuca et al, U.S. Pat. No. 5,843,928 all of which are hereby incorporated by reference in their entirety and for all purposes as if fully set forth herein.

Phosphine oxide III is a convenient reagent that can be used to prepare a large number of 19-nor-vitamin D compounds and is prepared according to the procedures described by Sicinski et al., J. Med. Chem., 41, 4662 (1998), DeLuca et al., U.S. Pat. No. 5,843,928; Perlman et al., Tetrahedron Lett. 32, 7663 (1991); and DeLuca et al., U.S. Pat. No. 5,086,191 which are hereby incorporated by reference in their entirety as if fully set forth herein.

The overall process of the synthesis of compound I is illustrated and described more completely in U.S. Pat. No. 5,843,928 entitled “2-Alkylidene-19-Nor-Vitamin D Compounds” and in U.S. Pat. No. 7,238,681, entitled “2-Methylene-18,19-Dinor-1α-Hydroxy-Homopregnacalciferol and Its Uses” the specifications of which are specifically incorporated herein by reference. 

We claim:
 1. 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form.
 2. The crystalline form of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol having molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90°, β=90° and γ=90°.
 3. A three dimensional structure for 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol as defined by the molecular packing arrangement set forth in claim
 2. 4. A method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of: (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate; (b) adding hexane to said solvent and dissolved product to form a mixture; (c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) separating the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.
 5. The method of claim 4 wherein the step of separating comprises filtering the mixture and precipitate to obtain the crystals.
 6. The method of claim 4 including a further step (d) comprising repeating steps (a) through (c) using the recovered crystals from step (c) as the product of step (a).
 7. The method of claim 4 wherein a ratio of ethyl acetate and hexane is about 1:99, by volume.
 8. A method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of: (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene; (b) providing a second solvent comprising hexane; (c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) recovering the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals.
 9. The method of claim 8 wherein a ratio of benzene and hexane is about 13:87, by volume.
 10. The method of claim 8 wherein the step of recovering comprises filtering to obtain the crystals.
 11. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place in a closed system purged with argon.
 12. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place at room temperature. 